JP2012134362A - Semiconductor light-emitting device package and light-emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a semiconductor light-emitting device package which solves problems related to power reduction caused by a long-term use of a semiconductor light-emitting device and separation between the package and an encapsulation material thereby achieving high durability.SOLUTION: A semiconductor light-emitting device package includes at least a resin molding containing (A) a base resin and (B) a filler, and the resin molding has the following characteristics: after 5.4 g of a green phosphor (Ba,Sr,Eu)SiOis preheated for one hour by 30 g of hot water at 95°C, 5 mm×5 mm×1 mm of the resin molding is added to the green phosphor and further heated for one hour at 95°C, the drawn resin molding is thoroughly cleansed by flowing water, and the cleansed resin molding is soaked in 0.5 g of demineralized water (pH 7.0) for 40 hours, pH of a water phase is 8.7 or less.

Description

  The present invention relates to an optical device, in particular, a package used for a semiconductor light emitting device including a light emitting element such as a light emitting diode, and a light emitting device.

  As shown in FIG. 1, a semiconductor light emitting device including a semiconductor light emitting element includes a semiconductor light emitting element 1, a resin molded body 2, a bonding wire 3, a sealing material 4, a lead frame 5 and the like, and a package mainly includes a lead frame 5 and the like. Conductive metal wiring and an insulating resin molded body 2.

  Conventionally, an insulating material used for a resin molding has generally been used in which a white pigment is blended with a thermoplastic resin such as polyamide (see, for example, Patent Document 1). A semiconductor light-emitting device that requires directivity for light emission is not limited to light emitted from a semiconductor light-emitting element in a target direction, but other light is transmitted through metal wiring such as a resin molded body and a lead frame, and a reflective material. The light is reflected in the target direction to increase luminous efficiency. Since a thermoplastic resin such as polyamide is translucent, a white pigment is blended into the resin when reflected by the resin molding, and the difference between the refractive index of the resin and the white pigment is utilized to remove the light from the semiconductor light emitting device. The light is reflected to increase the luminous efficiency of the semiconductor light emitting device.

  In Patent Document 1, even when a white pigment is used, depending on the type of the white pigment, its reflection efficiency is not sufficient, and light rays that are absorbed and transmitted are also emitted. As a result, light from the semiconductor light emitting element is emitted. In some cases, the efficiency of the semiconductor light emitting device may be reduced without being able to concentrate in the intended direction.

  In addition, in the package using polyamide, polyamide is a thermoplastic resin, and due to environmental problems, lead-free solder having a high melting point is actively used and the reflow temperature tends to increase. Therefore, there is a problem with heat resistance. In addition, since light degradation and thermal degradation occur due to ultraviolet rays and heat in polyamide, a light emitting element having a light emitting region up to a high energy wavelength region such as a blue to near ultraviolet semiconductor light emitting element which has been practically used in recent years was used. In this case, deterioration due to light becomes a particular problem. In the present situation where a brighter light emitting element is demanded, the problem of thermal degradation and light degradation becomes more obvious due to the large light flux and heat generated from the semiconductor light emitting element.

  Therefore, for the purpose of enhancing heat resistance, ceramics containing sintered alumina have been developed as insulating package materials (see, for example, Patent Document 2). Packages using ceramics have good heat resistance, but a high-temperature sintering process is required after molding during manufacturing. In the sintering process, cost problems such as electricity costs, and the size of the compact due to sintering Because of the change in shape, defective products are likely to be produced and there is a problem in mass productivity.

  Furthermore, in recent years, a case has been proposed in which a polyorganosiloxane is used as a resin and a silicone resin composition using titanium oxide as a white pigment is molded (see, for example, Patent Document 3). By using polyorganosiloxane as the resin, heat resistance is improved as compared with those using polyamide.

JP 2002-283498 A JP 2004-288937 A JP 2009-155415 A

In the semiconductor light emitting device, heat is generated from the semiconductor light emitting element, and particularly when a bright light emitting element is used , not only the light but also the amount of generated heat is increased. Therefore, the environment in which the resin molded body constituting the package of the semiconductor light emitting device is placed by heat generation and light emission from the semiconductor light emitting element becomes increasingly severe. Although the package using ceramics and the package using silicone resin that have been developed in recent years are considerably improved in the durability compared with the package using the conventional thermoplastic resin, the long-term use of the light emitting device It has not been sufficient to cope with the problem of reduced output and the problem of peeling between the package and the sealing material.

  In order to solve the above problems, the inventors have conducted extensive research, and the effects of heat generation and light emission from the semiconductor light emitting element are excited not only by the package of the semiconductor light emitting device but also by light from the semiconductor light emitting element. It has been found that the phosphor is present in the phosphor that emits light, and an environment in which a deteriorated phosphor easily exists. And the deterioration thing of this fluorescent substance turns into a strong alkaline substance, and since the deterioration of a package arises with the alkali, the knowledge that the fall of light emission output and the problem of peeling arise was acquired. The present invention has been made under such circumstances, and improves and solves problems related to reduction in output caused by long-term use of a semiconductor light-emitting device and peeling of a package and a sealing material, and a highly durable semiconductor light-emitting device. The purpose is to provide a package.

As a result of intensive studies to solve the above problems, the present inventors have used the above-mentioned problems by using a package for a semiconductor light-emitting device in which phosphor degradation products that are alkaline substances are difficult to be captured in the package surface and the microstructure thereof. It was found that can be solved. In addition, it has also been found that such a package is a highly durable package for a semiconductor light emitting device irrespective of the presence or absence of a phosphor degradation product.
That is, the present invention is as follows.
(A) A package for a semiconductor light emitting device comprising at least a resin molded body containing a base resin and (B) filler,
A package for a semiconductor light-emitting device, wherein an alkali component hardly remains on a surface of a resin molded body or in a resin molded body when the resin molded body is heat-treated in water together with a phosphor.

Specifically, a package for a semiconductor light emitting device comprising at least a resin molded body containing (A) a base resin and (B) a filler, and the resin molded body has the following characteristics.
5.4 g of green phosphor (Ba, Sr, Eu) ₂ SiO ₄ was previously heated with 30 g of hot water of 95 ° C. for 1 hour, and the resin molded body of 5 mm × 5 mm × 1 mm square was put therein and further heated to 95 ° C. After heating for 1 hour, the taken-out resin molded body is sufficiently washed with running water, and the washed resin molded body is immersed in 0.5 g of demineralized water (pH 7.0) for 40 hours. pH is 8.7 or less.

In the resin molded body, the number of the (B) filler having a particle diameter of 0.2 μm or more and 50 μm or less contained per 100 μm ^{2 in} cross section of the resin molded body is preferably 100 or more and 350 or less.
Moreover, it is preferable that the said resin molding contains polyorganosiloxane as said (A) base resin, and also contains (C) a curing catalyst.

  The (B) filler preferably contains alumina, and the (B) filler is preferably surface-treated.

  Moreover, it is preferable that the weight ratio of said (A) base resin and said (B) filler contained in the said resin molding is 15-60: 85-40 (however, the whole quantity shall be 100).

  The resin molded body preferably has a light reflectance of 60% or more at a wavelength of 460 nm and a light reflectance of 50% or more at a wavelength of 400 nm at a thickness of 0.3 mm. The resin molded body preferably has a Shore D hardness of 25 or more and 75 or less as defined in JIS K 6253.

  The resin molded body preferably further contains a compound having an alicyclic hydrocarbon group, and the resin molded body is consistently 45 ° C. or lower as an operating temperature before molding and 300 ° C. It is preferable to manufacture by molding at the following temperature.

  Another aspect of the present invention is a semiconductor light emitting device including at least a semiconductor light emitting element, the package described above, a phosphor, and a sealing material.

  According to the present invention, it is possible to provide a highly durable package for a semiconductor light-emitting device that is less likely to cause a decrease in output caused by long-term use of the semiconductor light-emitting device and peeling of the package and the sealing material.

It is a conceptual diagram showing the one aspect | mode of the semiconductor light-emitting device of this invention. It is a conceptual diagram showing the one aspect | mode of the semiconductor light-emitting device of this invention. It is the figure which observed the cross section of the resin molding which comprises the package of this invention with the scanning electron microscope (SEM) (drawing substitute photograph). It is a graph which shows the result of having performed the lighting durability test of the semiconductor light-emitting device using the package of this invention. It is a figure which shows the adhesive evaluation result with the sealing material of a package of this invention, and a lead frame (drawing substitute photograph). It is a figure showing the surface of the resin molding before the deterioration test of the resin molding by a fluorescent substance degradation thing (drawing substitute photograph). It is a figure showing the surface of the resin molding after the deterioration test of the resin molding by a fluorescent substance degradation thing (drawing substitute photograph).

<1. Resin molding>
The package for a semiconductor light-emitting device of the present invention includes at least a resin molded body containing (A) a base resin and (B) a filler. The resin molded body used in the present invention is characterized in that an alkali component generated when heat-treated in water together with a phosphor hardly remains on the surface of the resin molded body or in the resin molded body.
In general, a semiconductor light-emitting device includes a semiconductor light-emitting element and a phosphor that emits fluorescence of a specific wavelength when excited by light from the semiconductor light-emitting element, together with a package. Many phosphors used in semiconductor light emitting devices are known to deteriorate due to heat from the semiconductor light emitting element. And since fluorescent substance deteriorates, the function which absorbs excitation light and emits fluorescence falls, and the brightness | luminance of a semiconductor light-emitting device falls. However, it has not been known that the degradation product of the phosphor has an adverse effect on the package and the reflectance of the package is lowered and the adhesiveness between the package and the sealing material is lowered. The present invention has been made based on such new findings.

  The present invention solves the problem of a package for a semiconductor light-emitting device by the relationship of phosphor degradation products. That is, the resin molded body of the present invention is hardly deteriorated even when used together with various phosphors that are likely to become strong alkaline substances when deteriorated, and can be a package having extremely high heat / light reliability when used as a package. In addition, the semiconductor light-emitting device package of the present invention also has an effect of high durability even in a situation where there is no phosphor degradation product.

<1-1. Residual test of phosphor degradation product on resin molding>
The resin molded body included in the semiconductor light emitting device package of the present invention is 5.4 g of green phosphor (Ba, Sr, Eu) ₂ SiO ₄ , previously heated with 30 g of hot water at 95 ° C. for 1 hour, and then 5 mm × 5 mm. A 1 mm square resin molded product was added and further heated at 95 ° C. for 1 hour, and then the taken out resin molded product was sufficiently washed with running water, and the washed resin molded product was washed with 0.5 g of demineralized water (pH 7. The pH of the aqueous phase after being immersed in 0) for 40 hours is 8.7 or less.

The resin molding to be used for the residual test is obtained by molding a raw material (resin composition) of a resin molding, which will be described later, to a thickness of 0.3 mm or 1.0 mm, for example, and applying heat energy or light energy to cure. It is. In the present invention, a resin molded body obtained by curing a resin composition before curing at 150 ° C. for 3 minutes under a pressure of 10 kg / cm ² and further post-curing at 200 ° C. for 10 minutes is used for the test.
Curing in the present invention means a state change from a state showing fluidity to a state showing no fluidity. For example, even if the object is left to stand for 30 minutes in a state tilted 45 degrees from the horizontal, it is completely fluid. It is assumed that it has been cured.

  Based on the new knowledge that the phosphor deteriorates into a strong alkaline substance, and the alkali causes deterioration of the package, resulting in a decrease in light emission output and a problem of peeling, a specific characteristic is obtained by the above residual test. The present inventors have come up with a resin molded body having the following characteristics. When a resin molded body is heat-treated in water with a phosphor, the phenomenon that an alkali component hardly remains on the surface of the resin molded body or in the resin molded body is a case where it is used as a package used in a semiconductor light emitting device using a phosphor together. In addition, it means that the package itself is hardly deteriorated even if it is lit for a long time under high temperature and high humidity, and corrosion of the metal used for the electrode can be reduced.

Green phosphor (Ba, Sr, Eu) ₂ SiO ₄ is one of those widely used as LED phosphors for television backlights and lighting fixtures, and these phosphors are used as packages and sealing materials. Is required not to deteriorate even in a state of contact for a long time. By heating the green phosphor (Ba, Sr, Eu) ₂ SiO ₄ , the green phosphor deteriorates to become an alkaline substance, and when heated again with the resin molded body, the alkaline substance derived from the phosphor becomes a resin molded product. It becomes easy to be absorbed by the body. After washing, the alkaline substance adhering to the surface of the resin molded body and the alkaline substance adsorbed on the resin molded body are eluted in water by immersing in water for 40 hours, so the pH of the aqueous phase is measured. Thus, it is possible to measure the ease of adhering or adsorbing the alkaline substance on the resin molded body. In addition, demineralized water (pH 7.0) is used as the water to be immersed after washing the resin molded body.
Demineralized water can be prepared by a method using an ion exchange resin. Moreover, you may use a commercially available thing. The pH can be measured with a pH meter.

  When the pH of the aqueous phase is 8.7 or less, the resin molded body hardly adheres to or adsorbs the alkaline substance, and the resin molded body is hardly deteriorated due to the alkaline substance. Therefore, problems such as reduction in brightness and peeling do not occur. On the other hand, when the pH of the aqueous phase is greater than 8.7, that is, a more alkaline aqueous phase, the resin molded body has adhered or adsorbed many alkaline substances, and the resin molding caused by the alkaline substances Problems such as body brightness reduction and peeling are likely to occur. The pH of the aqueous phase is more preferably 8.5 or less.

  In order for the resin molded body to satisfy the above requirements, it is important to select an appropriate base resin, the type and shape of the filler, and the amount ratio between the base resin and the filler.

  Specifically, for example, polyorganosiloxane is used as (A) base resin, and (B) filler preferably contains alumina, and the weight ratio of base resin to filler is 15 to 60:85 to 40 (however, the total amount) Is preferably 100).

  Furthermore, in order for the resin molded body to satisfy the above requirements, it is generally required that the surface of the cured material is not rough or has no small holes, and for that purpose, the crosslinking points in the resin are uniformly dispersed, It is preferable to have a structure in which the cross-linking points are connected by a long linear molecular chain. Specifically, the weight average molecular weight is usually 500 or more and 200,000 or less, preferably 700 or more and 100,000 or less, more preferably 900 or more and 10,000 or less, and a vinyl group having vinyl groups only at both ends. A method using a silicone obtained by addition polymerization of an organosiloxane and a polyorganosiloxane having a hydrosilyl group randomly in the molecule is effective.

<1-2. Reflectivity of resin molding>
As long as the resin molding which comprises the package of this invention is used as a package for semiconductor light-emitting devices, it is preferable that a high reflectance can be maintained about ultraviolet-visible light. The reflectance of light having a wavelength of 460 nm at a thickness of 0.3 mm is preferably 60% or more, more preferably 80% or more, and still more preferably 90% or more.
Further, the reflectance of light having a wavelength of 400 nm at a thickness of 0.3 mm is preferably 50% or more, more preferably 70% or more, and further preferably 90% or more.
The reflectance of the resin molding can be controlled by (A) the type of base resin, (B) the type of filler, particle size, content, and the like.

<1-3. Refractive index of resin molding>
The resin molded body constituting the package of the present invention does not contain (B) filler, that is, (A) 1.41 to 1.54 as the refractive index of the molded body cured by adding an additive to the base resin as necessary. It is preferable that When the refractive index of the base resin is in such a range, the reflection loss of light at the interface between the resin molded body and the sealing material can be suppressed due to the balance with the resin used for the sealing material.
The refractive index of the resin molding can be controlled by the type of (A) base resin and the functional group and content contained in the resin. Specifically, the refractive index can be increased by including a phenyl group as a functional group, and the functional group can be decreased by containing fluorine. Incidentally, about 0.8 (mol) of phenyl group content is added to dimethyl polyorganosiloxane having no phenyl group (refractive index: 1.40 to 1.41) with respect to the number of Si (mol number). It is known that the refractive index reaches approximately 1.53 to 1.54.
Also, particles such as alumina (refractive index: 1.7), zinc oxide (refractive index: 2.0), zirconia (refractive index: 2.4), titania (refractive index: 2.7) are added as fillers. It is also possible to increase the refractive index.

<1-4. Hardness of resin molding>
The resin molded body constituting the package of the present invention preferably has a Shore D hardness of 25 or more and 75 or less. The Shore D hardness is obtained by quantifying the amount of deformation by using a type D durometer and pressing an indenter into the surface of the resin molded body in accordance with JIS K6253.
By setting the Shore D hardness of the resin molded body within this range, the resin molded body of the present invention has elasticity like rubber and has a restoring force that returns to its original state even when deformed by heat or external force. . Therefore, even when incorporated in a semiconductor light-emitting device, even when the amount of heat generated from the semiconductor light-emitting element is large, the force generated at the interface due to the difference in coefficient of linear expansion between the metal and the resin molded body is absorbed, and the metal wiring from the resin molded body It becomes difficult to peel off. In addition, since such a resin molding tends to be hard to adhere a phosphor degradation product, adhesion to a sealing material containing a resin and a phosphor layer is also improved.
The Shore D hardness of the resin molded body can be controlled within the above range by adjusting the crosslink density of the resin or adjusting the amount of filler (white pigment or the like) contained in the resin molded body.

<2. Raw material of resin molding>
The resin molding used for the package for semiconductor light emitting devices of the present invention can be obtained by molding a resin composition containing (A) a base resin and (B) a filler.
<2-1. (A) Base resin>
The (A) base resin contained in the resin molded body constituting the package of the present invention may be a thermoplastic resin as long as the pH of the aqueous phase measured by the above method with respect to the resin molded body is 8.7 or less. A thermosetting resin may be used, and the type thereof is not particularly limited. Thermoplastic resins include aromatic polyamide resin, polyphthalamide resin (PPA), sulfone resin, polyamideimide resin (PAI), polyketone resin (PK), polycarbonate resin (PC), polyphenylene sulfide (PPS), liquid crystal Polymer (LCP), ABS resin, PBT resin, etc. can be used. Moreover, as a thermosetting resin, an epoxy resin, a modified epoxy resin, a silicone resin, a modified silicone resin, an acrylate resin, a urethane resin, etc. can be used. Among these, it is preferable to use a silicone resin from the viewpoint of heat resistance and the like.

When a silicone resin is used as the base resin (A) in the resin molded body of the present invention, polyorganosiloxane is preferably used.
The polyorganosiloxane refers to a polymer substance in which an organic group is added to a structure having a portion in which a silicon atom is bonded to another silicon atom through oxygen. Usually, it refers to an organic polymer having a siloxane bond as the main chain, and examples thereof include compounds represented by the following general composition formula (1) and mixtures thereof.
(R ¹ R ² R ³ SiO _1/2 ) _M (R ⁴ R ⁵ SiO _2/2 ) _D (R ⁶ SiO _3/2 ) _T (SiO _4/2 ) _Q (1)
Here, in the above formula (1), R ¹ to R ⁶ are independently selected from an organic functional group, a hydroxyl group, and a hydrogen atom. M, D, T, and Q are 0 to less than 1 and satisfy M + D + T + Q = 1.

  The polyorganosiloxane may be liquid or solid at room temperature and normal pressure, but is more preferably liquid. The normal temperature refers to a temperature in the range of 20 ° C. ± 15 ° C. (5-35 ° C.), and the normal pressure refers to a pressure equal to atmospheric pressure, which is approximately 1 atm.

  When the polyorganosiloxane is classified according to the curing mechanism, polyorganosiloxanes such as an addition polymerization curing type, a condensation polymerization curing type, an ultraviolet curing type, and a peroxide crosslinking type can be generally mentioned. Among these, addition polymerization curing type (addition type polyorganosiloxane) and condensation polymerization curing type (condensation type polyorganosiloxane) are preferable. In particular, there is no generation of by-products (not preferred because it increases the pressure in the molding container or remains as foam in the cured material) during the molding process, and the reaction is not reversible (addition polymerization). More preferred are the types of addition-type polyorganosiloxanes that cure by:

  The addition-type polyorganosiloxane refers to a polyorganosiloxane chain crosslinked by an organic addition bond. As a typical one, for example, a silicon-containing compound having (A1) alkenyl group such as vinylsilane and a silicon compound containing (A2) hydrosilyl group such as hydrosilane has a total hydrosilyl group amount of 0.5 times or more, A compound having an Si—C—C—Si bond at the cross-linking point obtained by mixing in an amount ratio of 2.0 times or less and (C) reacting in the presence of an addition condensation catalyst such as a Pt catalyst as a curing catalyst. Can be mentioned.

(A1) As a silicon-containing compound having an alkenyl group, the following general formula (2)
R _n SiO _{[(4-n) / 2]} (2)
And an organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule.
In the above formula (2), R is the same or different substituted or unsubstituted monovalent hydrocarbon group, alkoxy group, or hydroxyl group, and n is a positive number satisfying 1 ≦ n <2.
In the silicon-containing compound having the (A1) alkenyl group, the alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms such as a vinyl group, an allyl group, a butenyl group, or a pentenyl group. When R is a hydrocarbon group, it is selected from an alkyl group such as a methyl group or an ethyl group, a monovalent hydrocarbon group having 1 to 20 carbon atoms such as a vinyl group or a phenyl group. Preferably, they are a methyl group, an ethyl group, and a phenyl group.
When UV resistance is required, about 65% of R in the above formula is preferably a methyl group. That is, the number of functional groups other than methyl groups is preferably about 0.5 (mole) with respect to the number of Si (mole number). More preferably, 80% or more is a methyl group. R may be an alkoxy group having 1 to 8 carbon atoms or a hydroxyl group, but the content of the alkoxy group or hydroxyl group is preferably 10% or less of the weight of the silicon-containing compound having (A1) alkenyl group. Further, n is a positive number satisfying 1 ≦ n <2, but if this value is 2 or more, sufficient strength cannot be obtained for bonding between the packaging material and a conductor such as a lead frame, and is less than 1. It becomes difficult to synthesize this organopolysiloxane.

  Examples of the silicon-containing compound having the (A1) alkenyl group include vinyl silane and vinyl group-containing polyorganosiloxane. These may be used alone or in combination of two or more in any ratio and combination. it can. Among these, a vinyl group-containing polyorganosiloxane having two or more vinyl groups in the molecule is preferable.

Specific examples of the vinyl group-containing polyorganosiloxane having two or more vinyl groups in the molecule include the following.
Both ends vinyl polydimethylsiloxane DMS-V00, DMS-V03, DMS-V05, DMS-V21, DMS-V22, DMS-V25, DMS-V31, DMS-V33, DMS-V35, DMS-V41, DMS-V42, DMS-V46, DMS-V52 (both manufactured by Gelest)
Both-end vinyldimethylsiloxane-diphenylsiloxane copolymer PDV-0325, PDV-0331, PDV-0341, PDV-0346, PDV-0525, PDV-0541, PDV-1625, PDV-1631, PDV-1635, PDV-1641, PDV -2331, PDV-2335 (both manufactured by Gelest)
Both end vinylphenylmethylsiloxane PMV-9925 (manufactured by Gelest)
Trimethylsilyl-blocked vinylmethylsiloxane-dimethylsiloxane copolymer VDT-123, VDT-127, VDT-131, VDT-153, VDT-431, VDT-731, VDT-954 (all manufactured by Gelest)
Vinyl T-structure polymer VTT-106, MTV-124 (both manufactured by Gelest)

  Examples of the silicon compound containing (A2) hydrosilyl group include hydrosilane and hydrosilyl group-containing polyorganosiloxane, and these may be used alone or in combination of two or more in any ratio and combination. Can do. Of these, hydrosilyl group-containing polyorganosiloxane having two or more hydrosilyl groups in the molecule is preferred.

Specific examples of the polyorganosiloxane containing two or more hydrosilyl groups in the molecule include the following.
Both terminal hydrosilyl polydimethylsiloxane DMS-H03, DMS-H11, DMS-H21, DMS-H25, DMS-H31, DMS-H41 (all manufactured by Gelest)
Both end trimethylsilyl-blocked methylhydrosiloxane-dimethylsiloxane copolymer HMS-013, HMS-031, HMS-064, HMS-071, HMS-082, HMS-151, HMS-301, HMS-501 (all manufactured by Gelest)

  The amount of the silicon-containing compound having (A1) alkenyl group and the silicon compound having (A2) hydrosilyl group used in the present invention is (A2) hydrosilyl group with respect to 1 mol of silicon-containing compound having (A1) alkenyl group. Is usually 0.5 mol or more, preferably 0.7 mol or more, more preferably 0.8 mol or more. Moreover, it is 2.0 mol or less normally, Preferably it is 1.8 mol or less, More preferably, it is 1.5 mol or less. By reacting at such a ratio, the remaining amount of unreacted end groups after curing is reduced, and there is little change over time such as coloring and peeling during lighting use, and a cured product with a smooth surface Obtainable.

  In order to make it difficult for the alkali component to be trapped on the surface of the resin molded body or in the resin molded body, it is also important to set the number of reaction points (crosslinking points) causing hydrosilylation within a controlled range. Specifically, both the alkenyl group and the hydrosilyl group are preferably 0.15 mmol / g or more and 20 mmol / g or less in 1 g of the base resin containing no filler. More preferably, it is 0.25 mmol / g or more and 10 mmol / g or less.

  Further, the viscosity of the base resin (A) before the filler is added is preferably 100,000 mPa · s or less at room temperature because of easy handling. More preferably, it is 20,000 mPa · s or less. More preferably, it is 10,000 mPa · s or less. The lower limit is not particularly limited, but is generally 15 mPa · s or more in relation to volatility (boiling point).

Furthermore, it is preferable that the weight average molecular weight by gel permeation chromatography measured using polystyrene of (A) base resin as a standard substance is 500 or more and 100,000 or less. More preferably, it is 700 or more and 50,000 or less. Furthermore, it is more preferably 900 or more for the purpose of reducing volatile components (to maintain adhesion to other members) and 10,000 or less for ease of handling of the material before molding. Most preferably, it is 5,000 or less.

  Examples of the condensed polyorganosiloxane include a compound having a Si—O—Si bond obtained by hydrolysis and polycondensation of an alkylalkoxysilane at a crosslinking point. Specific examples include polycondensates obtained by hydrolysis and polycondensation of compounds represented by the following general formula (3) and / or (4) and / or oligomers thereof.

SiX _n Y ¹ _4-n (3)
In formula (3), X represents a hydrolyzable group, Y ¹ represents a monovalent organic group, and n represents an integer of 1 or more representing the number of X groups. However, 4 ≧ n.

(SiX _t Y ¹ _3-t ) _u Y ² (4)
In formula (4), X represents a hydrolyzable group, Y ¹ represents a monovalent organic group, Y ² represents a u-valent organic group, t represents an integer of 3 or less, and u is 2 or more. Represents an integer.

  As the condensed polyorganosiloxane, known ones can be used. For example, JP 2006-77234 A, JP 2006-291018 A, JP 2006-316264 A, JP 2006-336010 A, The semiconductor light-emitting device members described in JP-A-2006-348284 and International Publication No. 2006/090804 are suitable.

Preferred materials among the condensed polyorganosiloxanes are described below.
When polyorganosiloxane is used in a semiconductor light emitting device in general, the adhesion to the semiconductor light emitting element, the substrate on which the semiconductor element is arranged, the metal wiring, etc. may be weak. Therefore, in particular, a condensed polyorganosiloxane having one or more features among the following [1] and [2] is preferable.
[1] The silicon content is 20% by weight or more.
[2] The measured solid Si-nuclear magnetic resonance (NMR) spectrum has at least one peak derived from Si in the following (a) and / or (b).
(A) A peak whose peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less with reference to silicone rubber, and the peak half-value width is 0.3 ppm or more and 3.0 ppm or less.
(B) A peak whose peak top position is in a region where the chemical shift is −80 ppm or more and less than −40 ppm with respect to the silicone rubber, and the half width of the peak is 0.3 ppm or more and 5.0 ppm or less.

In the present invention, a polyorganosiloxane having the following feature [3] in addition to the above features [1] and [2] may be used.
[3] It has a phenyl group.
In addition to improving the strength of the material by using a polyorganosiloxane having a phenyl group, the refractive index increases, so the resin molded body and the sealing material Light reflection loss at the interface can be suppressed. In particular, when the average number of phenyl groups is 0.8 (mole) or less with respect to the number (mole) of Si contained in one molecule of the polyorganosiloxane represented by the above (1), resin molding The difference between the refractive index of the body and the refractive index of the white filler can be increased, and the difference in refractive index with the sealing resin can be reduced, further reducing the reflection loss of light at the interface between the resin molded body and the sealing material. Since it can suppress, it is still more preferable. The refractive index of a resin material that does not contain a specific white filler is preferably in the range of 1.41 to 1.54.

  In addition, among the polyorganosiloxanes having the above characteristics, addition-type polyorganosiloxane that does not have a component that is eliminated as the reaction progresses is moldable when cured in a closed mold. From the standpoint of heat resistance (small weight change), etc., it is preferable. Condensation type polyorganosiloxane can also be used when the molding process does not significantly affect the molding processability of the components generated with the progress of the condensation reaction. Condensed polyorganosiloxanes having a content of from 01% by weight to 10% by weight are preferred. More preferably, the silanol content is 3% by weight or less.

<2-2. (B) Filler>
As (B) filler used for this invention, the well-known inorganic or organic filler which does not inhibit hardening of resin can be selected suitably.
In the cross-sectional observation of the resin molded body, the filler is contained in the resin molded body so that the number of fillers having a particle size of 0.2 μm or more and 50 μm or less contained per 100 μm ² is 100 or more and 350 or less. It is preferable.

  A resin molded body used for a package of a semiconductor light emitting device is generally manufactured by blending a filler with a base resin for the purpose of maintaining strength. When such a resin molded body is processed for a package, the filler is likely to be exposed on the fracture surface generated when the conventional resin is processed. If the resin with the exposed filler is used for a long period of time, the resin is deformed by heat generated from the semiconductor light emitting element, and a gap is formed between the filler and the resin, so that it is easy to adsorb contaminants such as phosphor degradation products. . As a result, the present inventors have found that the luminance of the light emitting device decreases. Then, the present inventors have conceived to prevent a decrease in luminance caused by exposure of the filler by controlling the number of fillers present on the fracture surface of the resin molded body.

  Among the fillers contained in the resin molded body, even if they are present, there is almost no influence on the physical property improving effect of the resin molded body of the present invention even if they are present because of their small size and surface area. Further, if the thickness is 0.2 μm or less, the diameter of the filler is too small and the contribution to the effect of the present invention is almost eliminated. Therefore, the number of fillers of 0.2 μm or more and 50 μm or less is important.

In the cross-sectional observation of the resin molded body, when the number of fillers included per cross section of 100 μm ² exceeds 350, the amount of the exposed filler is large, and the luminance of the light emitting device decreases due to long-term use. The material becomes brittle. Therefore, when such a resin molded body is used as a package, there is a tendency that a light emitting device having long-term reliability is not obtained.
On the other hand, when the number of fillers is less than 100, the content of the filler is too small, so the package using such a resin molded body does not have a sufficient function as a reflector, and as a result It tends to cause a decrease in luminance.
From the viewpoint of having further long-term reliability, in the cross-sectional observation of the resin molded body, the number of fillers having the above-mentioned particle size contained per 100 μm ² of the resin molded body cross section is more preferably 120 to 300, More preferably, it is 280.

A method for measuring the white pigment contained in the resin molded body will be described below.
As a specific method for cross-sectional observation, a scanning electron microscope (SEM, SEM-EDX), an X-ray photoelectron spectrometer (ESCA), a transmission battery microscope (TEM), or the like is preferably used.

Among them, SEM or ESCA is preferably used from the intention of observing particles having a particle size of 0.2 μm or more over a certain area.
Among them, SEM observation is preferable from the viewpoint of simplicity of measurement.

  The SEM observation of the cross section of the resin molded body can be performed by the method described in the examples.

Further, the inventors have also found that the number of fillers in the cross section of the resin molded body can be controlled by the adhesiveness between the resin molded body and the filler. That is, when the adhesiveness between the resin molded body and the filler is good, it has been found that the filler on the fracture surface of the resin molded body is covered with the film of the resin molded body and is not easily exposed.
The number of fillers contained per 100 μm ² of the cross section of this resin molded body is controlled by the amount of the adsorptive functional group contained in the base resin, the surface treatment for adjusting the activity level of the filler surface, and the inclusion of a viscosity modifier. can do. For example, a general control method is to introduce in advance functional groups that can form chemical bonds such as a covalent bond, a hydrogen bond, or a coordinate bond with each other on the surface of the base resin and the filler.

Examples of the inorganic filler that can be used in the present invention include metal oxides such as alumina (aluminum oxide), silicon oxide, titanium oxide (titania), zinc oxide, and magnesium oxide; calcium carbonate, barium carbonate, magnesium carbonate, barium sulfate, Metal salts such as aluminum hydroxide, calcium hydroxide, magnesium hydroxide; boron nitride, alumina white, colloidal silica, aluminum silicate, zirconium silicate, aluminum borate, clay, talc, kaolin, mica, synthetic mica .
In addition, examples of the organic filler include resin particles such as fluorine resin particles, guanamine resin particles, melamine resin particles, acrylic resin particles, and silicone resin particles, but they are not limited to these.

  Among these, the white pigment which exhibits white from the function as a reflecting material is preferable. In particular, the absorption of visible light is weak and the refractive index is preferably high, and specifically, titania, alumina and the like are particularly preferable. When the light emission wavelength of the light emitting element is 410 nm or less, alumina, zirconium oxide, or the like, which has little light absorption in the ultraviolet to near ultraviolet region, is preferable. From the viewpoint of thermal conductivity, alumina and boron nitride are preferable. A filler can be used individually or in mixture of 2 or more types.

The alumina may be in any crystal form, but α-alumina having characteristics such as chemically stable, high melting point, high mechanical strength, high hardness, and high electric insulation resistance can be preferably used.
In addition, when an element other than aluminum and oxygen is contained in alumina as an impurity, it is not preferable because it absorbs the visible light region and is colored. Preferably, the chromium, iron and titanium contents are each 0.02% or less, more preferably 0.01% or less. Further, in order to increase the thermal conductivity, it is preferable to use alumina having a purity of 98% or more, particularly 99% or more, and particularly preferably low soda alumina.

Specific examples of titania include TA-100, TA-200, TA-300, TA-500, and TR-840 manufactured by Fuji Titanium Industry. Specific examples of alumina include A30 series manufactured by Nippon Light Metal Co., Ltd. , AN series, A40 series, MM series, LS series, AHP series, “Admafine Alumina” manufactured by Admatechs, AO-5 type, AO-8 type, CR series manufactured by Nihon Bikosky Co., Ltd. Aldrich 10 μm ² diameter alumina powder, Showa Denko A-42 series, A-43 series, A-50 series, AS series, AL-43 series, AL-47 series, AL-160SG series, A-170 Series, AL-170 series, AM series made by Sumitomo Chemical, L series, AMS series, AES series, AKP series, AA series, etc. are listed. Specific examples of zirconia include UEP-100 manufactured by Daiichi Rare Chemicals Co., Ltd., and specific examples of zinc oxide include Hakusuitec. 2 types of zinc oxide manufactured by the company are listed.

  The filler preferably has an aspect ratio of 1.0 to 4.0, and more preferably 1.0 to 3.0. When the aspect ratio is in the above range, high reflectivity is likely to be manifested by scattering, and the reflection of light having a short wavelength in the near ultraviolet region is particularly large.

Moreover, when using a white pigment as said filler, it is preferable that a primary particle diameter is 0.1 micrometer or more and 2 micrometers or less. The lower limit is preferably 0.15 μm or more, more preferably 0.2 μm or more, and the upper limit is preferably 1 μm or less, more preferably 0.8 μm or less, and particularly preferably 0.5 μm or less.
If the primary particle diameter is too small, the scattered light intensity is small and the reflectance tends to be low. If the primary particle diameter is too large, the scattering intensity is large but the forward scattering tendency tends to be low, so the reflectance is small. Tend to be. A white pigment having a primary particle size larger than 2 μm can be used in combination for the purpose of increasing the filling rate of the white pigment in the resin composition.

On the other hand, the white pigment preferably has a median diameter (D ₅₀ ) of secondary particles of 0.2 μm or more and 50 μm or less, and more preferably has an upper limit of 5 μm or less. A white pigment having a secondary particle size larger than 50 μm can be used in combination for the purpose of increasing the filling rate of the white pigment in the resin composition.

  The primary particle in the present invention refers to the smallest unit particle that can be clearly distinguished from other particles constituting the powder, and the primary particle size refers to the particle size measured by observation with an electron microscope such as SEM. . On the other hand, particles formed by agglomeration of primary particles are called secondary particles. The secondary particle size is not limited to observation with an electron microscope such as SEM. It can be measured by using a particle size analyzer or the like. The particle diameter or particle diameter described in the present specification refers to the secondary particle diameter unless otherwise specified. When there is a variation in the particle diameter, several points (for example, 10 points) are observed with an SEM, and the average value can be obtained as the particle diameter. In the measurement, when the particle diameter is not spherical, the longest length, that is, the length of the long axis is taken as the particle diameter.

The filler is preferably subjected to a surface treatment in order to improve adhesion with the base resin. Examples of the surface treatment agent include coupling agents such as a silane coupling agent and a titanium coupling agent.
Specifically, epoxy-functional alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, amino-functional alkoxysilanes such as N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. It is preferable to use a mercapto functional alkoxysilane.

  The surface treatment with the coupling agent may be performed by a normal method, and the method is not particularly limited. For example, a method in which a silane coupling agent is dissolved in a suitable solvent, a filler is immersed in this solution, the solvent is distilled off, and heat drying is exemplified.

  Moreover, phosphor content in the resin molded body is such that the weight ratio of the base resin to the filler is 15 to 60:85 to 40 (where the total amount is 100), so that the phosphor deterioration product is a resin molded body. It becomes difficult to be trapped on the surface or the resin molded body, and as a result, a semiconductor light emitting device with little deterioration during lighting for a long time can be obtained. The range of the weight ratio of the content is more preferably 30-40: 70-60.

Furthermore, glass fiber, glass fiber, glass powder, or the like can be used as part of the filler for the purpose of increasing the strength of the molded body.
Preferred glass fibers, glass fibers, and glass powders include, for example, Denka's large particle size silica FB-40S, Central Glass's EFDE50-31, EGP200-10, EFH75-10, NSG Vetrotex's REV1, REV7, and REV8. Is mentioned.

By appropriately selecting the amount and type of the above-mentioned materials such as fillers, the resin concentration on the surface of the resin molded body may be relatively lowered, or the surface properties may be changed in some cases.
As a result, when a semiconductor light emitting device is formed, the possibility of contact between a resin molded body and a phosphor, particularly a deteriorated product exhibiting strong alkalinity, can be reduced, and durability can be improved. Prolonging the life of the light emitting device can be expected.

<2-3. (C) Curing catalyst>
The curing catalyst in the present invention is a catalyst for curing (A) the base resin. By adding a curing catalyst, the polymerization reaction is accelerated and cured.

  When the resin molding of the present invention is a silicone resin, there are an addition polymerization catalyst and a condensation polymerization catalyst depending on the curing mechanism of the polyorganosiloxane. The addition polymerization catalyst is a catalyst for promoting the hydrosilylation addition reaction between the alkenyl group in the component (A1) and the hydrosilyl group in the component (A2). Examples of the addition polymerization catalyst include , Platinum black, platinous chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, complex of chloroplatinic acid and olefins, platinum catalyst such as platinum bisacetoacetate, palladium catalyst, rhodium And platinum group metal catalysts such as system catalysts. The amount of addition polymerization catalyst is usually 1 ppm or more, preferably 2 ppm or more, and usually 500 ppm or less, preferably 100 ppm or less, based on the total weight of the above components (A1) and (A2) as a platinum group metal. Preferably it is 20 ppm or less. As a result, the curing reaction rate can be maintained at a high level, and at the same time, the cost is reduced due to the use of a large amount of expensive metal catalyst, and the durability of the material is reduced due to the remaining active catalyst species (coloration during heating and storage) UV resistance, etc.) can be avoided.

As the polycondensation catalyst, acids such as hydrochloric acid, nitric acid, sulfuric acid and organic acids, alkalis such as ammonia and amines, metal chelate compounds and the like can be used, and Ti, Ta, Zr, Al, Hf are preferable. A metal chelate compound containing any one or more of Zn, Sn, and Pt can be used. Among them, the metal chelate compound preferably contains one or more of Ti, Al, Zn, and Zr, and more preferably contains Zr.
These catalysts are selected in consideration of the stability of the semiconductor light emitting device package material, the hardness of the coating, the non-yellowing property, the curability and the like.

The blending amount of the polycondensation catalyst is usually preferably 0.01 to 10% by weight, preferably 0.05 to 6% by weight based on the total weight of the components represented by the above formulas (3) and (4). It is more preferable that
When the addition amount is in the above range, the curability, storage stability, and package quality of the semiconductor light emitting device package material are good. If the amount added is higher than the upper limit value, there may be a problem in the storage stability of the package material. If the amount added is lower than the lower limit value, the curing time becomes longer, the package productivity decreases, and the package quality tends to deteriorate due to uncured components. .

<2-4. Other ingredients>
In the resin composition of this invention, unless it deviates from the summary of this invention, another component can be contained by 1 type or 2 types or more in arbitrary ratios and combinations as needed.
For example, silica fine particles having a particle diameter of less than 0.2 μm can be contained for the purpose of controlling fluidity of the resin composition and suppressing sedimentation of the white pigment. Such silica fine particles do not correspond to the filler in the present invention.
The content of the silica fine particles is usually 60 parts by weight or less, preferably 40 parts by weight or less based on 100 parts by weight of the polyorganosiloxane when the base resin is silicone.
The silica fine particles used in the present invention are not particularly limited, but the specific surface area by the BET method is usually 0.02 m ² / g or more, preferably 10 m ² / g or more, more preferably 50 m ² / g or more. More preferably, it is 100 m ² / g or more. Moreover, it is 500 m < ² > / g or less normally, Preferably it is 200 m < ² > / g or less. If the specific surface area is too small, the effect of adding silica fine particles cannot be obtained, and if it is too large, dispersion in the resin becomes difficult. As the silica fine particles, for example, those obtained by reacting a silanol group on the particle surface with a surface modifier to make the surface hydrophobic may be used.

  Examples of the surface modifier include alkylsilane compounds, and specific examples include dimethyldichlorosilane, hexamethyldisilazane, octylsilane, and dimethylsilicone oil.

Examples of the silica fine particles include fumed silica. The fumed silica oxidizes and hydrolyzes silicon tetrachloride (SiCl ₄ ) gas with a flame of 1100 to 1400 ° C. in which a mixed gas of hydrogen and oxygen is burned. Manufactured by decomposing. The primary particles of fumed silica are spherical ultrafine particles mainly composed of amorphous silicon dioxide (SiO ₂ ) having an average particle size of about 5 to 50 nm. Secondary particles of several hundred nm are formed. Since fumed silica is an ultrafine particle and is produced by rapid cooling, the surface structure is in a chemically active state.

  Examples of such fumed silica include “Aerosil” (registered trademark) manufactured by Nippon Aerosil Co., Ltd. Examples of hydrophilic Aerosil (registered trademark) include “90”, “130”, “150”. , “200”, “300”, and hydrophobic Aerosil (registered trademark) include “R8200”, “R972”, “R972V”, “R972CF”, “R974”, “R202”, “R805”, “R805” R812 "," R812S "," RY200 "," RY200S "," RX200 ".

In order to improve the scratch resistance by setting the Shore D hardness of the molded article obtained by molding the resin composition to an appropriate value, a crosslinking agent can be added. As the crosslinking agent, for example, a compound represented by the following general formula (6) and / or a partial hydrolysis-condensation product thereof is preferably used.
R ⁷ _a SiX _4-a (6)
In the above formula (6), R ⁷ is an unsubstituted or substituted monovalent hydrocarbon group, X is a hydrolyzable group, and a is 0 or 1.

In the general formula (6), the unsubstituted or substituted monovalent hydrocarbon group represented by R ⁷ is, for example, 10 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, preferably 1 -8, particularly preferably 1-6 lower alkyl groups;
Alkenyl groups such as vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group; (meth) acryloyl group;
(Meth) acryloyloxy group;
A cycloalkyl group such as a cyclohexyl group;
Aryl groups such as phenyl, tolyl and naphthyl;
Aralkyl groups such as benzyl group and 2-phenylethyl group;
And a group in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms, for example, chloromethyl group, 3,3,3-trifluoropropyl group, etc. 1 to 8, particularly preferably 1 to 6. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group and a phenyl group are preferable, and a methyl group and a phenyl group are particularly preferable.

  In the general formula (6), examples of the hydrolyzable group represented by X include alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group, ketoxime groups such as methylethyl ketoxime group, and alkenyl such as isopropenoxy group. Examples include an acyloxy group such as an oxy group and an acetoxy group, and an aminoxy group such as a dimethylaminoxy group. An alkoxy group is preferable, and a methoxy group and an ethoxy group are particularly preferable.

  Specific examples of the compound represented by the general formula (6) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, and vinyltrimethoxysilane. , Trifunctional alkoxysilanes such as phenyltrimethoxysilane and methyltris (methoxyethoxy) silane; tetrafunctional alkoxysilanes such as tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane; methyltripropenoxysilane, methyltriacetoxysilane, Vinyltriacetoxysilane, methyltri (butanoxime) silane, vinyltri (butanoxime) silane, phenyltri (butanoxime) silane, propyltri (butanoxime) silane, tetra (butanoxime) Silane, 3,3,3-trifluoropropyltri (butanoxime) silane, 3-chloropropyltri (butanoxime) silane, methyltri (propanoxime) silane, methyltri (pentanoxime) silane, methyltri (isopentanoxime) silane, vinyltri ( Cyclopentanoxime) silane, methyltri (cyclohexanoxime) silane and partial hydrolysis condensates thereof, and the like, preferably alkoxysilanes and partial hydrolysis condensates thereof.

  When the base resin (A) is a silicone resin, the amount of the crosslinking agent contained in the resin composition is preferably 0 to 30 parts by mass, more preferably 100 parts by mass of the polyorganosiloxane. Is 0 to 20 parts by mass, particularly preferably 0 to 10 parts by mass. When the blending amount is more than 30 parts by mass, the hardness of the resin cured product is increased, the surface smoothness is lowered, and the alkali component tends to be easily captured on the surface of the resin molded body or the resin molded body.

  It is also preferable to add a rubbery elastic body such as powdered silicone rubber in order to increase the elasticity of the resin molded body and obtain desired physical characteristics. The addition amount is preferably 0 to 30 parts by mass, more preferably 0 to 20 parts by mass, and particularly preferably 0 to 5 parts by mass with respect to 100 parts by mass of the resin molded body. When the blending amount is more than 30 parts by mass, the strength expressed by the entanglement of the polymer molecules becomes small, and the molded article becomes brittle.

  Moreover, in order to adjust characteristics, such as the hardening speed of the molded object obtained from a resin composition, and the surface state of hardened | cured material, a hardening retarder (catalyst control agent) can also be added. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide, and these may be used in combination.

  Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols such as 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne and 1-ethynyl-1-cyclohexanol. And maleate esters such as ene-yne compounds and dimethyl malate. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide and the like. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

  Among these curing retardants, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, and 1-ethynyl-1-cyclohexanol are preferable because they have good delay activity and are easily available. .

As the addition amount of the curing retardant, the lower limit of the preferable addition amount per mole of the (C) curing catalyst to be used is 10 ⁻¹ mol, more preferably 1 mol, and the upper limit is 10 ³ mol, more preferably 50 Is a mole. Moreover, these hardening retarders may be used independently and may be used together 2 or more types.

It is also preferable to add a compound having an alicyclic hydrocarbon group in order to adjust the physical properties of the molded article. Examples of the compound having an alicyclic hydrocarbon group include a silane coupling agent having a cyclohexyl group or a norbornyl group, and a cyclohexane-based organic compound having a vinyl group, and trivinylcyclohexane, vinylcyclohexane, and vinylnorbornene are particularly preferable. .
The content of the compound having an alicyclic hydrocarbon group can be appropriately set, but is preferably 0 to 10 parts by weight per 100 parts by weight of the resin molded body.

In order to increase the strength and toughness of the resin composition after thermosetting, inorganic fibers such as glass fibers may be included. In order to increase thermal conductivity, boron nitride and aluminum nitride having high thermal conductivity are included. In addition to the above-mentioned white pigment, fibrous alumina or the like can be contained. In addition, for the purpose of lowering the linear expansion coefficient of the cured product, quartz beads, glass beads and the like can be contained.
If the addition amount is too small, the desired effect cannot be obtained, and if it is too large, the viscosity of the resin composition increases and affects the workability, so that a sufficient effect is exhibited and the workability of the material is not impaired. The selection may be made as appropriate. Usually, it is 100 parts by weight or less, preferably 60 parts by weight or less with respect to 100 parts by weight of the polyorganosiloxane.

  In addition, the resin composition includes other ion migration (electrochemical migration) inhibitors, curing accelerators, curing retarders, anti-aging agents, radical inhibitors, ultraviolet absorbers, adhesion improvers, flame retardants, interfaces. Activator, Storage stability improver, Ozone degradation inhibitor, Light stabilizer, Thickener, Plasticizer, Coupling agent, Antioxidant, Thermal stabilizer, Conductivity imparting agent, Antistatic agent, Radiation blocker, Nuclear An agent, a phosphorus peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a physical property adjusting agent and the like can be contained within a range not impairing the object and effect of the present invention.

  In addition to these, addition of a coupling agent is also preferable from the viewpoint of further controlling the physical properties of the molded body. A part of the coupling agent includes, for example, a silane coupling agent as described in part of the filler surface modifier and the crosslinking agent.

<3. Method for producing resin molded body of the present invention>
Examples of the molding method of the resin molded body of the present invention include a compression molding method, a transfer molding method, and an injection molding method.

  The resin molded body is preferably manufactured by molding at a temperature of 45 ° C. or lower consistently as an operation temperature before molding and less than 300 ° C.

  The compression molding method can be performed using a compression molding machine. The molding temperature may be appropriately selected according to the material, but is usually 80 ° C. or higher and 300 ° C. or lower, preferably 100 ° C. or higher and 250 ° C. or lower, and more preferably 130 ° C. or higher and 200 ° C. or lower. The molding time is appropriately selected according to the curing rate of the material, and is usually 3 seconds or more and 1200 seconds or less, preferably 5 seconds or more and 900 seconds or less, more preferably 10 seconds or more and 600 seconds or less.

  The transfer molding method can be performed using a transfer molding machine. The molding temperature may be appropriately selected according to the material, but is usually 80 ° C. or higher and 300 ° C. or lower, preferably 100 ° C. or higher and 250 ° C. or lower, and more preferably 130 ° C. or higher and 200 ° C. or lower. The molding time is appropriately selected according to the gelation speed and curing speed of the material, and is usually 3 seconds or more and 1200 seconds or less, preferably 5 seconds or more and 900 seconds or less, more preferably 10 seconds or more and 600 seconds or less.

  The injection molding method can be performed using an injection molding machine. The cylinder set temperature may be appropriately selected according to the material, but is usually 100 ° C. or lower, preferably 80 ° C. or lower, and more preferably 60 ° C. or lower. The mold temperature is 80 ° C. or higher and 300 ° C. or lower, preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 130 ° C. or higher and 200 ° C. or lower. The injection time varies depending on the material, but is usually several seconds or less than 1 second. The molding time is appropriately selected according to the gelation speed and curing speed of the material, and is usually 3 seconds or more and 1200 seconds or less, preferably 5 seconds or more and 900 seconds or less, more preferably 10 seconds or more and 600 seconds or less.

  In any molding method, post-curing can be performed as necessary, and the post-curing temperature is 100 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 250 ° C. or lower, more preferably 170 ° C. or higher and 200 ° C. or lower. It is. The post-curing time is usually 3 minutes or longer and 24 hours or shorter, preferably 5 minutes or longer and 10 hours or shorter, more preferably 10 minutes or longer and 5 hours or shorter.

  The resin molded body of the present invention can be made into a package for a semiconductor light-emitting device by molding together with metal wiring during molding. For example, a substrate having wiring as metal wiring is created, and a resin molded body is injection molded using a mold on the substrate, or a resin-molded body is injection molded by placing a lead frame on the mold as metal wiring. It can be manufactured by a method or the like.

<4. Semiconductor light emitting device>
The half-conductor light emitting device package of the present invention is usually used as a semiconductor light emitting device with a semiconductor light emitting element mounted thereon. The outline of the semiconductor light emitting device will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the gist of the present invention.
FIG. 1 shows an example of a semiconductor light emitting device, which includes a semiconductor light emitting element 1, a package made of a resin molded body 2 and a metal lead frame 5, a bonding wire 3, a sealing material 4, and the like.

The semiconductor light emitting device 1 uses a near ultraviolet semiconductor light emitting device that emits light having a wavelength in the near ultraviolet region, a purple semiconductor light emitting device that emits light in a purple region, a blue semiconductor light emitting device that emits light in a blue region, and the like. It emits light having a wavelength of 350 nm or more and 520 nm or less. Although only one semiconductor light emitting element is illustrated in FIG. 1, a plurality of semiconductor light emitting elements can be arranged in a linear shape or a planar shape. By arranging the semiconductor light emitting element 1 in a planar shape, surface illumination can be obtained, and this embodiment is suitable when it is desired to further increase the output.

  The resin molded body 2 forming the package is molded together with the lead frame 5. The shape of the package is not particularly limited and may be a planar type or a cup type, but is preferably a cup type from the viewpoint of imparting directivity to light. The lead frame 5 is made of a conductive metal, and plays a role of supplying power from outside the semiconductor light emitting device and energizing the semiconductor light emitting element 1.

  The bonding wire 3 fixes the semiconductor light emitting element 1 to the package. Further, when the semiconductor light emitting element 1 is not in contact with the lead frame serving as an electrode, the conductive bonding wire 3 plays a role of supplying an electrode to the semiconductor light emitting element 1. The bonding wire 3 is bonded to the lead frame 5 by applying pressure to the lead frame 5 and applying vibrations of heat and ultrasonic waves. However, when the surface of the lead frame 5 is made of silver or a silver alloy, the adhesiveness is improved, which is preferable.

The sealing material 4 is usually a mixture in which a phosphor is mixed with a binder resin, and the phosphor converts excitation light from the semiconductor light emitting element 1 into fluorescence. In the present embodiment, the sealing material also serves as the phosphor layer. The phosphor contained in the sealing material 4 is appropriately selected according to the wavelength of the excitation light of the semiconductor light emitting device 1. In a light emitting device that emits white light, if a semiconductor light emitting element that emits blue excitation light is used as an excitation light source, white light can be generated by including green and red phosphors in the phosphor layer. In the case of a semiconductor light emitting device that emits purple excitation light, there are cases where blue and yellow phosphors are included in the phosphor layer, and blue, green, and red phosphors are included in the phosphor layer. It is done.
As the binder resin contained in the sealing material 4, it is possible to appropriately select a translucent resin conventionally used in sealing materials, and epoxy resins, silicone resins, acrylic resins, polycarbonate resins, and the like are used. However, it is preferable to use a silicone resin.

  A mode in which the phosphor is not mixed with the sealing material 4 and only the role of sealing is performed and the phosphor layer is separately configured is also an embodiment of the present invention. For example, as shown in FIG. 2, a mode in which a transparent substrate (not shown) is prepared so as to cover the resin molded body 2 and the phosphor layer 6 is formed thereon is also conceivable. In the case of such an aspect, since the semiconductor light emitting element 1 and the phosphor layer 6 are arranged at a distance, the deterioration of the phosphor layer 6 can be prevented, and the output of the light emitting device can be improved. . The distance between the semiconductor light emitting element 1 and the phosphor layer 6 is preferably 1 to 500 mm, and more preferably 5 to 500 mm.

  In FIG. 1, the semiconductor light emitting element 1 is directly mounted on the resin molded body 2, and the thickness of the resin molded body 2 where the semiconductor light emitting element 1 is mounted is usually 100 μm or more, preferably 200 μm or more. . Moreover, it is 3000 micrometers or less normally, Preferably it is 2000 micrometers or less. If the thickness is too thin, light tends to be transmitted to the bottom surface and the reflectivity tends to decrease, which may cause problems such as insufficient strength of the package and deformation during handling. If it is too thick, the package itself is thick and bulky. Therefore, the application of the semiconductor light emitting device may be limited.

[Use in combination with phosphor particles]
As described above, the package for a semiconductor light emitting device according to the present invention solves the problem relating to the adverse effect of the deteriorated phosphor on the package, and the semiconductor light emitting device is preferably configured together with the phosphor. A wavelength converting member by applying and curing a sealing material (such as a curable epoxy or silicone resin) in which a phosphor is dispersed in the package of the present invention (molding / potting inside a semiconductor light emitting device cup (cup)) The output light from the semiconductor light emitting device can be dimmed. The phosphor may be used alone, or may be used in combination with two or more types of phosphors at an arbitrary ratio, for example, to produce a white semiconductor light emitting device.

[Phosphor]
The composition of the phosphor that can be used is not particularly limited, but a crystalline matrix (for example, a metal oxide such as Y ₂ O ₃ and Zn ₂ SiO ₄ , a phosphate such as Ca ₅ (PO ₄ ) ₃ Cl, or Sulfides such as ZnS, SrS and CaS) and rare earth metal ions such as Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb as activators or coactivators, or It is preferable to combine with metal ions such as Ag, Cu, Au, Al, Mn and Sb.

Preferred examples of the crystalline matrix include sulfides such as (Zn, Cd) S, SrGa ₂ S ₄ , SrS and ZnS, oxysulfides such as Y ₂ O ₂ S, (Y, Gd) ₃ Al ₅ O ₁₂ , YAlO ₃ , BaMgAl ₁₀ O ₁₇ , (Ba, Sr) (Mg, Mn) Al ₁₀ O ₁₇ , (Ba, Sr, Ca) (Mg, Zn, Mn) Al ₁₀ O ₁₇ , BaAl ₁₂ O ₁₉ , CeMgAl ₁₁ O ₁₉ , aluminates such as (Ba, Sr, Mg) O.Al ₂ O ₃ , BaAl ₂ Si ₂ O ₈ , SrAl ₂ O ₄ , Sr ₄ Al ₁₄ O ₂₅ and Y ₃ Al ₅ O ₁₂ , Y ₂ SiO Silicates such as ₅ and Zn ₂ SiO ₄ , oxides such as SnO ₂ and Y ₂ O ₃ , borates such as GdMgB ₅ O ₁₀ and (Y, Gd) BO ₃ , Ca ₁₀ (PO ₄ ) ₆ ( F, Cl) ₂ and (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ etc. Halophosphates and phosphates such as Sr ₂ P ₂ O ₇ and (La, Ce) PO ₄ .

  However, the crystalline matrix and the activator or coactivator described above are not particularly limited in terms of elemental composition, and they can be partially substituted by analog elements. And when the fluorescent substance obtained absorbs the light of ultraviolet region-visible region, it is useful when emitting visible light.

The following substances can be used as phosphors, but they are merely typical substances and fluorescent substances that can be used in the present invention, and are not limited thereto. In the following examples, phosphors having partially different structures are represented by an omitted method in some cases. For example, “Y ₂ SiO ₅ : Ce ³⁺ ”, “Y ₂ SiO ₅ : Tb ³⁺ ”, “Y ₂ SiO ₅ : Ce ³⁺ ”, and Tb ³⁺ are “Y ₂ SiO ₅ : Ce ³⁺ ”. , Tb ³⁺ , and “La ₂ O ₂ S: Eu”, “Y ₂ O ₂ S: Eu” and “(La, Y) ₂ O ₂ S: Eu” are “( La, Y) ₂ O ₂ S: Eu ″. Omitted positions are delimited by commas (,).

[Red fluorescent material]
The specific wavelength range of the fluorescence emitted by the phosphor emitting red fluorescence (hereinafter also referred to as “red phosphor”) is usually 570 nm or more, preferably 580 nm or more, and usually 700 nm or less, preferably 680 nm or less. It is.

Such a red phosphor is represented by (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu and is composed of destructive particles having a red fracture surface for emitting light in the red region. Ordered crystal growth to emit light in the red region, expressed as europium activated alkaline earth silicon nitride or (Y, La, Gd, Lu) ₂ O ₂ S: Eu It includes a europium activated rare earth oxychalcogenide phosphor composed of grown particles having a generally spherical shape.

  Further, it contains at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo disclosed in Japanese Patent Publication No. 2004-300247, and a part of Al element or Phosphors containing oxynitride and / or oxysulfide containing an α-sialon structure that is entirely replaced by Ga element can also be used in the embodiment of the present invention. This phosphor is a phosphor containing oxynitride and / or oxysulfide.

Other red fluorescent materials include Eu activated oxysulfide phosphors such as (La, Y) ₂ O ₂ S: Eu, Eu activations such as Y (V, P) O ₄ : Eu and Y ₂ O ₃ : Eu. Oxide phosphors, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Mn and (Ba, Mg) ₂ SiO ₄ : Eu, Mn activated silicate phosphors such as Eu, Mn, (Ca, Sr) S : Eu activated sulfide phosphor such as Eu, YAlO ₃ : Eu activated aluminate phosphor such as Eu, LiY ₉ (SiO ₄ ) ₆ O ₂ : Eu, Ca ₂ Y ₈ (SiO ₄ ) ₆ O ₂ : Eu (Sr, Ba.Ca) ₃ SiO ₅ : Eu and Sr ₂ BaSiO ₅ : Eu activated silicate phosphors such as Eu, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce and (Tb, Gd) ₃ Al ₅ O _12: Ce activation aluminate, such as Ce DOO phosphor, (Ca, Sr, Ba) 2 Si 5 N 8: Eu, (Mg, Ca, Sr, Ba) SiN 2: Eu and (Mg, Ca, Sr, Ba ) AlSiN 3: Eu activity such as Eu Nitride activated phosphor, Ce-activated nitride phosphor such as (Mg, Ca, Sr, Ba) AlSiN ₃ : Ce, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn Eu, Mn activated halophosphate phosphors such as (Ba ₃ Mg) Si ₂ O ₈ : EU, Mn and (Ba, Sr, Ca, Mg) ₃ (Zn, Mg) Si ₂ O ₈ : Eu, Mn, etc. Eu, Mn activated silicate phosphor, 3.5MgO.0.5MgF ₂ .GeO ₂ : Mn activated germanide phosphor such as Mn, Eu activated α-sialon: Eu activated oxynite such as Eu Ride phosphor (Gd, Y, Lu, La) ₂ O ₃ : Eu, Bi-activated oxide phosphors such as Eu and Bi, (Gd, Y, Lu, La) ₂ O ₂ S: Eu, Bi such as Eu and Bi Activated oxysulfide phosphor, (Gd, Y, Lu, La) VO ₄ : Eu, Bi-activated vanadate phosphor such as Eu, Bi, SrY ₂ S ₄ : Eu, Ce-activated sulfide fluorescence such as Eu, Ce Bodies, Ce activated sulfide phosphors such as CaLa ₂ S ₄ : Ce, (Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn and (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Mn activated phosphate phosphors such as Eu and Mn, (Y, Lu) ₂ WO ₆ : Eu, Mo activated tungstate phosphors such as Eu and Mo, (Ba, Sr, Ca) _x Si _y N _z : Eu, Ce (x, y, and z are 1 or More integer) Eu such, Ce-activated nitride phosphor, (Ca, Sr, Ba, Mg) 10 (PO 4) 6 (F, Cl, Br, OH): Eu, Eu , such as Mn, Mn activated halophosphate phosphor, and (Y, Lu, Gd, Tb ) 1-x Sc x Ce y) 2 (Ca, Mg) 1-r (Mg, Zn) 2 + r Si zq Ge q O 12+ δ Ce activated silicate phosphors such as can also be used.

  In addition, as the red phosphor, a rare earth element ion complex having an anion such as β-diketone salt, β-diketone, aromatic carboxylic acid and Bronsted acid as a ligand, perylene dye (for example, Dibenzo {[f, f ′]-4,4 ′, 7,7′-tetraphenyl} diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene), anthraquinone dye, lake Red organic phosphor containing dye, azo dye, quinacridone dye, anthracene dye, isoindoline dye, isoindolinone dye, phthalocyanine dye, triphenylmethane basic dye, indanthrone dye, indophenol dye, cyanine dye and dioxazine dye Can also be used.

Among them, a red phosphor having a maximum wavelength of 580 nm or more, preferably 590 nm or more and 620 nm or less, preferably 610 nm or less can be suitably used as an orange phosphor. Examples of such orange phosphors include (Sr, Ba) ₃ SiO ₅ : Eu, (Sr, Mg) ₃ (PO ₄ ) ₂ : Sn ²⁺ and SrCaAlSiN ₃ : Eu.

[Green phosphor]
The specific wavelength range of fluorescence emitted by a phosphor emitting green fluorescence (hereinafter also referred to as “green phosphor”) is usually 490 nm or more, preferably 500 nm or more, and usually 570 nm or less, preferably 550 nm or less. is there.

Such a green phosphor is represented by (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu and is composed of crushed particles having a crushed surface for emitting light in the green region. Alkaline earth silicon oxynitride and (Ba, Ca, Sr, Mg) SiO ₄ : Eu, composed of crushed particles with a crushed surface for emitting light in the green region A europium activated alkali silicate phosphor.

Other green phosphors include Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu and (Ba, Sr, Ca) Al ₂ O ₄ : Eu, (Sr, Ba) Al ₂ Si ₂ O ₈ : Eu, (Ba, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca, Mg) 2 SiO 4: Eu and _{(Ba, Sr, Ca) 2} (Mg, Zn) Si 2 O 7: Eu , such as Eu-activated silicate _{phosphor, Y 2 SiO 5: Ce,} Ce , such as Tb, Tb-activated silicate _{phosphor, Sr 2 P 2 O 7 -Sr} 2 B 2 O 5: Eu activated borate phosphate phosphor such as Eu , Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu-activated halosilicate phosphors such as Eu, Zn ₂ SiO ₄ : Mn-activated silicate phosphors such as Mn, CeMgAl ₁₁ O ₁₉ : Tb and Y ₃ Al ₅ O _12: Tb-activated aluminum, such as Tb Over preparative _{phosphor, Ca 2 Y 8 (SiO 4} ) 6: Tb and La ₃ Ga ₅ SiO _14: Tb-activated silicate phosphors such as Tb, (Sr, Ba, Ca ) Ga 2 S 4: Eu, Tb, Eu, Tb, Sm activated thiogallate phosphors such as Sm, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce and (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce-activated silicate phosphor such as Ce and Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce Ce activated oxide phosphors such as CaSc ₂ O ₄ : Ce, SrSi ₂ O ₂ N ₂ : Eu, (Sr, Ba, Ca) Si ₂ O ₂ N ₂ : Eu and Eu activated β-sialon and Eu activity Eu-activated oxynitriles such as activated α-sialon De _{phosphor, BaMgAl 10 O 17: Eu,} Eu , such as Mn, Mn-activated aluminate phosphor, SrAl ₂ O _4: Eu activation aluminate phosphor such as Eu, (La, Gd, Y ) 2 O 2 S: Tb-activated oxysulfide phosphors such as Tb, LaPO ₄ : Ce, Tb-activated phosphate phosphors such as Ce, Tb, Sulfide phosphors such as ZnS: Cu, Al and ZnS: Cu, Au, Al, Y, Ga, Lu, Sc, La) BO ₃ : Ce, Tb, Na ₂ Gd ₂ B ₂ O ₇ : Ce, Tb and (Ba, Sr) ₂ (Ca, Mg, Zn) B ₂ O ₆ : K, Ce, Tb activated borate phosphors such as Ce, Tb, Eu, Mn activated halosilicate phosphors such as Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu, Mn, (Sr, Ca, Ba) (Al, Ga, In) ₂ S ₄ : Eu-activated thioaluminate phosphors and thiogallate phosphors such as Eu, and (Ca, Sr) ₈ (Mg, Zn) (SiO ₄ ) ₄ Cl ₂ : Eu, Mn-activated halosilicate fluorescence such as Eu and Mn The body can also be used.

  Moreover, fluorescent substances such as pyridine-phthalimide condensed derivatives, benzoxazinone, quinazolinone, coumarin, quinophthalone and naphthalate imide, and organic phosphors such as terbium complex having hexyl salicylate as a ligand can also be used.

[Blue phosphor]
The specific wavelength range of the fluorescence emitted by the phosphor emitting blue fluorescence (hereinafter also referred to as “blue phosphor”) is usually 420 nm or more, preferably 440 nm or more, and usually 480 nm or less, preferably 470 nm or less. is there.

Such a blue phosphor is represented by BaMgAl ₁₀ O ₁₇ : Eu, and is composed of grown particles having a substantially hexagonal form as a regular crystal growth form for emitting light in the blue region. -Magnetic aluminate phosphor, (Ca, Sr, Ba) ₅ (PO ₄ ) ₃ Cl: Eu, a grown particle having a substantially spherical shape as a regular crystal growth form for emitting light in the blue region Europium-activated calcium halophosphate phosphor composed of: (Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: Eu, which is approximately cubic as a regular crystal growth form for emitting light in the blue region growth europium activated alkaline earth consists of particles aluminate phosphor having a shape and (Ca, Sr, Ba) Al 2 O 4: Eu or (Sr, Ca, Ba) l ₁₄ O _25: represented by Eu, including europium-activated alkaline earth aluminate phosphor composed of crushed particles having a crushed shape for emitting light in the blue region.

Other blue phosphors include Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, Eu activities such as Sr ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu and BaAl ₈ O ₁₃ : Eu. Activated aluminate phosphors, Ce-activated thiogallate phosphors such as SrGa ₂ S ₄ : Ce and CaGa ₂ S ₄ : Ce, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu and BaMgAl ₁₀ O ₁₇ : Eu Eu activated aluminate phosphor, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn activated aluminate phosphor such as Eu, Mn, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu and (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br.OH): Eu-activated halophosphate phosphors such as Eu, BaAl ₂ Si ₂ O ₈ : Eu and (Sr , B ) ₃ MgSi ₂ O _8: Eu activated silicate phosphor such as _{Eu, Sr 2 P 2 O 7} : Eu Eu -activated phosphate phosphor such as, ZnS: Ag and ZnS: Ag, sulfide phosphors such as Al, Y ₂ SiO ₅ : Ce-activated silicate phosphor such as Ce, tungstate phosphor such as CaWO ₄ , (Ba, Sr, Ca) BPO ₅ : Eu, Mn, (Sr, Ca) ₁₀ (PO ₄ ) ₆ · nB Eu, such as ₂ O ₃ : Eu and 2SrO.0.84P ₂ O ₅ .0.16B ₂ O ₃ : Eu, Mn activated boric acid phosphate phosphor and Eu such as Sr ₂ Si ₃ O ₈ .2SrCl ₂ : Eu Activated halosilicate phosphors can also be used.

  In addition, organic phosphors such as naphthalate imide, benzoxazole, coumarin, pyralizone and triazole compounds, and thulium complexes can also be used as blue phosphors.

  The average particle diameter (median diameter) of these phosphor particles is not particularly limited, but is usually 100 nm or more, preferably 2 μm or more, more preferably 5 μm or more, and usually 100 μm or less, preferably 50 μm or less, more preferably. Is 20 μm or less. The shape of the phosphor particles does not adversely affect the semiconductor light emitting device member, for example, does not adversely affect the fluidity of the phosphor portion forming liquid (liquid obtained by adding the phosphor to the semiconductor light emitting device member forming liquid). As long as it is not particularly limited.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited at all by the following example.

[Example 1]
In 58 mL of polyethylene ointment basket, 6.0 g of alumina (bulk density: 0.8 g / ml, average particle size: 1.2 μm, average aspect ratio: 1.48, purity: 99.12%), 0.25 g Surface-treated (trimethylsilyl-treated) fumed silica, phenyl group-free silicone (vinyl group: 0.3 mmol / g contained, platinum: 8 ppm contained, viscosity at room temperature: 3700 mPa · s. 3.04 g of a silicone containing no phenyl group (containing vinyl group: 0.1 mmol / g, hydrosilyl group: containing 4.6 mmol / g, viscosity at room temperature: 600 mPa · s). This silicone is referred to as “phenyl group-free silicone F”.) 0.30 g and a phenotype containing a cure retarding component (catalyst control component). Silicon group-free silicone (containing vinyl group: 0.2 mmol / g, hydrosilyl group: containing 0.1 mmol / g, alkynyl group: containing 0.2 mmol / g, 500 mPa · s. 0.15 g of “silicone G”.) Was added, and the mixture was stirred with Thinky's Awatori Kentaro ARV-200. 0.25 g of surface-treated (trimethylsilyl-treated) fumed silica was added again, and vacuum defoaming was performed with ARV-200 to obtain white resin composition 1.

The obtained white resin composition 1 was put into a stainless steel mold having a diameter of 1.3 cm and a thickness of 0.3 mm, 1.0 mm, and 3.0 mm, and the pressure was 10 kg / cm ² on a silver plate. Resin moldings 1 to 3 were obtained by heating and pressurizing at 150 ° C. for 3 minutes in the air, and further post-curing at 200 ° C. for 10 minutes in a ventilation dryer. In addition, the weight ratio of the base resin and the filler of the resin molded bodies 1 to 3 is 36.8: 63.2.

[Measurement of physical properties]
The obtained resin moldings 1 to 3 were measured for reflectance and hardness.
The reflectance was determined by measuring the reflectance of light having a wavelength of 400 nm and the reflectance of light having a wavelength of 460 nm using a SPECTROPHOMETER CM-2600d manufactured by Konica Minolta.
In addition, the hardness was measured according to JIS K6253 by using a durometer for Shore A hardness and Shore D hardness with respect to a laminate of two resin molded bodies 3 (3.0 mm thickness).

  The reflectance of the resin molded body 1 having a thickness of 0.3 mm was 94.2% under light irradiation of 400 nm and 94.3% under light irradiation of 460 nm. The hardness was 91 for Shore A and 33 for Shore D.

Samples molded to a thickness of 0.3 mm on a silver plate will not be peeled off or destroyed when removed from the mold, and then peeled off from the silver surface even if a slight force is applied from the side with a spatula. There was nothing to do or collapse.
In addition, the average number of fillers in the particle size range of 0.2 μm or more and 50 μm or less included in the cross section 100 μm ² of the resin molded body 1 was counted as 183. The measuring method was performed as follows using SEM S800 manufactured by HITACHI.
1) The resin molded body 1 was cut into small pieces with scissors.
2) It was embedded and fixed with a two-component curable epoxy.
3) Using an ultramicrotome UC6 and FC6 manufactured by Leica Microsystems, cutting was performed with a diamond knife at a set temperature of -120 ° C.
4) The etched surface was ion-etched with a self-made device.
5) Conductive treatment was performed with an osmium plasma coater manufactured by Philgen.
6) Observation was performed with SEM S800 manufactured by HITACHI.
7) The number of particles having a diameter of 0.2 μm or more and 50 μm or less in 100 μm ² was counted.
A state observed with an SEM is shown in FIG.

[Example 2]
1.75 g of phenyl group-free silicone (vinyl group: 1.2 mmol / g contained, platinum: 6.8 ppm contained, this silicone is referred to as “phenyl group-free silicone H”), phenyl group-free silicone ( 1.75 g of vinyl group: 0.3 mmol / g contained, hydrosilyl group: 1.8 mmol / g contained (this silicone is referred to as “phenyl group-free silicone I”) was used (normal temperature after mixing both silicones) The resin molded bodies 4 (thickness 0.3 mm), 5 (thickness 1.0 mm), and 6 (thickness 3.0 mm) were prepared in the same manner as in Example 1 except that the viscosity was 1460 mPa · s. . In addition, the weight ratio of the base resin and the filler of the resin molded body is 36.8: 63.2.

  When the physical properties of the resin molded body 4 were measured in the same manner as in Example 1, the reflectance of the resin molded body 4 having a thickness of 0.3 mm was 94.6% under light irradiation of 400 nm and 94 under light irradiation of 460 nm. It was 6%. The hardness of the resin molded body 6 having a thickness of 3.0 mm was 90 or more for Shore A and 40 for Shore D.

[Comparative Example 1]
A commercially available silicone-based packaging material whose hardness is increased so that Shore D is 90 or more by making spherical silica having a diameter of several μm to 100 μm and titania as a white pigment into 80% by weight or more in the resin molding as a total filler. Was molded under the same conditions as in Example 1 to obtain a resin molded body 7 (1.0 mm thick).

[Comparative Example 2]
A ceramic LED package (M5050N (KA-6)) manufactured by Kyoritsu Elex Co., Ltd. is used as the molded body 8 of Comparative Example 2.

[Comparative Example 3]
A molded product of polyphthalamide (Amodel A4122) manufactured by Solvay Advanced Polymers is used as a resin molded product 9 of Comparative Example 3.

[Phosphor deterioration test]
Put 50g of degassed demineralized water and 5.4g of green phosphor (Ba, Sr, Eu) ₂ SiO ₄ into a 50 mL flask equipped with a Dimroth, stirring blade and thermocouple, and heat the inner temperature at 95 ° C for 1 hour. The operation was performed. At that time, the pH of the green phosphor dispersion water was measured and found to be 14 or more. The resin molded bodies 2, 5 and 7 having a thickness of 1.0 mm obtained in Examples 1 and 2 and Comparative Example 1 were cut into 5 mm × 5 mm squares (0.05 g) and 5 mm ×, respectively. Each of the packages of Comparative Example 2 having a thickness of 5 mm × 1 mm (referred to as molded body 8) (0.06 g (with a lead frame)) was added, and the mixture was again heated and stirred at an internal temperature of 95 ° C. for 1 hour. Each molded body was taken out, washed for 2 minutes under sufficient running water, and immersed in 0.5 g of demineralized water (pH 7.0) in a 10 cc screw tube. After 40 hours, the pH of 0.5 g of water was measured with a HORIBA pH meter (twin pHB211), and the pH of the water into which the molded bodies 2 and 5 produced in Example 1 and Example 2 were charged was: Both were 8.7, the pH of the water in which the molded body 7 obtained in Comparative Example 1 was charged was 8.8, and the pH of the water in which the molded body 8 of Comparative Example 2 was charged was 8.9. Met. As compared with the comparative example, it was proved that the alkaline component derived from the phosphor degradation product hardly remained on the surface or inside of the molded body of the example.

[Durability evaluation test]
The white resin composition obtained in Example 2 was subjected to heat injection molding together with a copper lead frame plated with silver on the entire surface, thereby forming a recess having a length of 5 mm × width 5 mm × height 1.5 mm and an opening diameter of 3.6 mm. A cup-shaped surface-mount package was formed to obtain a package 1. Moreover, the PPA package (package 2) using the resin molding 9 of the comparative example 3 of the same shape as this was prepared, and the lighting durability test of LED was implemented.
Mounting of a semiconductor light emitting device (406 nm emission wavelength, rated current 20 mA) is performed by placing a silicone die bond material (KER-3000-M2 manufactured by Shin-Etsu Chemical Co., Ltd.) at a predetermined position on the inner lead exposed in the recess of the package. The silicone die bond material was cured at 100 ° C. for 1 hour and further at 150 ° C. for 2 hours.

Next, the sealing material was manufactured.
Momentive Performance Materials Japan G.K., both ends silanol dimethyl silicone oil XC96-723 385g, methyltrimethoxysilane 10.28g and zirconium tetraacetylacetonate powder 0.791g as a catalyst, stirring blade And a 500 ml three-necked flask equipped with a fractionating tube, a Dimroth condenser, and a Liebig condenser, and stirred for 15 minutes at room temperature until coarse particles of the catalyst were dissolved. Thereafter, the temperature of the reaction solution was raised to 100 ° C. to completely dissolve the catalyst, and initial hydrolysis was performed while stirring at 500 rpm for 30 minutes at 100 ° C. under total reflux.
Subsequently, the distillation outlet is switched to the Liebig condenser side, nitrogen is blown into the liquid with SV20, and methanol, water, and low-boiling silicon components of by-products are distilled off accompanying nitrogen, at 100 ° C. and 500 rpm for 1 hour. Stir. The polymerization reaction was continued for 5 hours while raising and maintaining the temperature at 130 ° C. while blowing nitrogen into the liquid with SV20 to obtain a reaction liquid having a viscosity of 120 mPa · s. Here, “SV” is an abbreviation for “Space Velocity” and refers to the volume of blown volume per unit time. Therefore, SV20 refers to blowing N ₂ in a volume 20 times that of the reaction solution in one hour.
Nitrogen blowing was stopped and the reaction solution was once cooled to room temperature, and then transferred to an eggplant-shaped flask. Methanol and moisture remaining in a minute amount at 120 ° C. and 1 kPa on an oil bath using a rotary evaporator, The low boiling silicon component was distilled off to obtain a solvent-free sealing material liquid having a viscosity of 230 mPa · s at room temperature.

  After dripping the obtained silicone sealing material liquid into the package recesses of the package 1 and the package 2 so as to be the same height as the upper edge of the opening, 90 ° C. for 2 hours, then 110 ° C. for 1 hour in a thermostatic chamber, The semiconductor light emitting device was sealed by performing heat curing at 150 ° C. for 3 hours.

The lighting endurance test is performed by setting the above-mentioned sealed packages 1 and 2 on a lighting power source on a 3 mm-thick heat-dissipating aluminum plate with a heat conductive insulating sheet, and an environmental testing machine at a temperature of 60 ° C. and a relative humidity of 90%. A continuous lighting test was conducted by applying a drive current of 60 mA. The semiconductor light emitting device was taken out every predetermined time, and the percentage of output over time (output maintenance rate) with respect to the initial output (mW) was measured offline (luminance measurement was 20 mA energization). The measurement results are shown in FIG.
As shown in FIG. 4, when the package 1 of Example 2 was used, it was found that the output retention rate was clearly higher than when the package 2 of Comparative Example 3 was used.

  Further, the package 1 of Example 2 and the package 2 of Comparative Example 3 are stored for 24 hours in an atmosphere of 85 ° C. and 85% RH (relative humidity), and immediately after taking out from the atmosphere, on a hot plate of 260 ° C. Then, a test for confirming the adhesion (peeling) between the sealing material and the package surface or the lead frame surface was also conducted. As a result, as shown in FIG. 5, peeling was recognized only in the case of the package 2 made of PPA (polyphthalamide) of Comparative Example 3.

[Adhesion evaluation test]
For the package 1 of Example 2, the package 2 of Comparative Example 3, and the ceramic LED package of Comparative Example 2 created in the durability test, the adhesion between the lead frame and the resin molded body by the following method ( A confirmation experiment of peeling was performed.
First, each package was washed with ethanol and dried. Next, a test penetrant (Color Check Penetrant FP-S (red) manufactured by Taseto Co., Ltd.) was sprayed on the dried package and allowed to stand for 5 minutes. About the package after standing, the liquid of the surface was wiped off with a wiper, further cleaned with ethanol, and dried at room temperature for 1 hour.

The package treated by the above procedure was observed for the next peeling.
(I) The metal and the resin are peeled off, and the coloring of the resin is observed.
(Ii) Further, Taseto Co., Ltd., a color check developer is sprayed thinly and left for 10 minutes to check the red color that emerges to confirm the presence or absence of peeling.
In the case of the observation of the above (i) and the observation of the above (ii), in the case of the package 1 derived from Example 2, no red color was observed between the lead frame and the resin molded body. On the other hand, in the case of the package 2 derived from the comparative example 3 and the ceramic package derived from the comparative example 2, both the red color was confirmed and it was found that peeling occurred between the lead frame and the resin molded body or the ceramic material. . That is, it was found that the package 1 is a package that hardly peels even when there is no influence of deterioration due to the phosphor.

[Deterioration test of molded resin with phosphor degradation product]
The resin molded body 2 obtained in Example 1, the resin molded body 5 obtained in Example 2, the resin molded body 7 obtained in Comparative Example 1, and the resin molded body 8 in Comparative Example 2 were each blue fluorescent. Body (BaMgAl ₁₀ O ₁₇ : Eu): green phosphor ((Ba, Sr, Eu) ₂ SiO ₄ ): red phosphor ((Sr _0.8 Ca _0.2 ) AlSiN ₃ : Eu) = 80.4: 10.5: When embedded in a phosphor mixture mixed at 9.1 (weight ratio), heated at 200 ° C. for 98 days, taken out and washed with water, as shown in FIG. 6 and FIG. Only in the case of, a trace of deterioration was observed.

[Discussion]
From these results, it is possible to obtain a resin molded body package in which phosphor degradation products are hard to be captured on the package surface and its fine structure according to the present invention. By using such a package, the semiconductor light emitting device can be used for a long time. It has been found that it is possible to provide a highly durable semiconductor light emitting device which is less likely to cause a decrease in output and peeling of a package and a sealing material.

DESCRIPTION OF SYMBOLS 1 Semiconductor light-emitting device 2 Resin molding 3 Bonding wire 4 Sealing material 5 Lead frame 6 Phosphor layer

Claims (12)

A package for a semiconductor light-emitting device, comprising at least a resin molded body containing (A) a base resin and (B) a filler, wherein the resin molded body has the following characteristics.
5.4 g of green phosphor (Ba, Sr, Eu) ₂ SiO ₄ was previously heated with 30 g of hot water of 95 ° C. for 1 hour, and the resin molded body of 5 mm × 5 mm × 1 mm square was put therein and further heated to 95 ° C. After heating for 1 hour, the taken-out resin molded body is sufficiently washed with running water, and the washed resin molded body is immersed in 0.5 g of demineralized water (pH 7.0) for 40 hours. pH is 8.7 or less. 2. The resin molded body according to claim 1, wherein the number of the (B) filler having a particle diameter of 0.2 μm or more and 50 μm or less contained per 100 μm ^{2 in} cross section of the resin molded body is 100 or more and 350 or less. The package for semiconductor light-emitting devices of description.   3. The package for a semiconductor light emitting device according to claim 1, wherein the resin molding includes polyorganosiloxane as the base resin (A) and further includes (C) a curing catalyst. 4.   The said (B) filler contains an alumina, The package for semiconductor light-emitting devices of any one of Claims 1-3 characterized by the above-mentioned.   The package for a semiconductor light emitting device according to claim 1, wherein the filler (B) is surface-treated.   In the resin molded body, the weight ratio of the (A) base resin and the (B) filler contained in the resin molded body is 15 to 60:85 to 40 (provided that the total amount is 100). The package for a semiconductor light-emitting device according to claim 1, wherein:   The package for a semiconductor light-emitting device according to claim 1, wherein the resin molded body has a thickness of 0.3 mm and a light reflectance of a wavelength of 460 nm is 60% or more.   The package for a semiconductor light-emitting device according to claim 1, wherein the resin molded body has a light reflectance of 50% or more at a wavelength of 400 nm at a thickness of 0.3 mm.   The package for a semiconductor light-emitting device according to claim 1, wherein the resin molded body has a Shore D hardness of 25 or more and 75 or less as defined in JIS K 6253.   The package for a semiconductor light-emitting device according to claim 1, wherein the resin molded body further includes a compound having an alicyclic hydrocarbon group.   The said resin molding is 45 degrees C or less consistently as operation temperature before a shaping | molding process, and is manufactured by the shaping | molding process at the temperature of 300 degrees C or less, The any one of Claims 1-10 characterized by the above-mentioned. A package for a semiconductor light emitting device according to the item.   A semiconductor light-emitting device comprising at least a semiconductor light-emitting element, the package for a semiconductor light-emitting device according to claim 1, a phosphor, and a sealing material.